U.S. patent number 11,045,794 [Application Number 16/323,671] was granted by the patent office on 2021-06-29 for supported catalyst used for synthesizing polyether amine, and manufacturing method.
This patent grant is currently assigned to Wanhua Chemical Group Co., Ltd.. The grantee listed for this patent is Wanhua Chemical Group Co., Ltd.. Invention is credited to Hao Ding, Zhanyu Gao, Weiqi Hua, Qingmei Jiang, Xin Li, Yuan Li, Zhenguo Liu, Zhipeng Liu, Shujie Ren, Jinhong Song, Lei Tang, Cong Wang, Xiaolong Wang, Jian Wu, Congying Zhang.
United States Patent |
11,045,794 |
Ren , et al. |
June 29, 2021 |
Supported catalyst used for synthesizing polyether amine, and
manufacturing method
Abstract
A supported catalyst used for synthesizing a polyether amine,
and a manufacturing method of the catalyst. The catalyst comprises:
a porous oxide as a support; Ni, Cu, Pd, and Rh as active
components; and one or more of any of Zr, Cr, Mo, Fe, Zn, Sn, Bi,
Ce, La, Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge and related metals
as an auxiliary agent. The catalyst can be used in an amination
reaction for a large molecular weight polyether polyol, and is
particularly active and selective for an amination reaction of a
low molecular weight polyether polyol. The catalyst has a simple
and economic manufacturing technique and good potential for future
applications.
Inventors: |
Ren; Shujie (Shandong,
CN), Zhang; Congying (Shandong, CN), Li;
Xin (Shandong, CN), Liu; Zhenguo (Shandong,
CN), Wang; Xiaolong (Shandong, CN), Tang;
Lei (Shandong, CN), Liu; Zhipeng (Shandong,
CN), Gao; Zhanyu (Shandong, CN), Wu;
Jian (Shandong, CN), Wang; Cong (Shandong,
CN), Li; Yuan (Shandong, CN), Jiang;
Qingmei (Shandong, CN), Song; Jinhong (Shandong,
CN), Hua; Weiqi (Shandong, CN), Ding;
Hao (Shandong, CN) |
Applicant: |
Name |
City |
State |
Country |
Type |
Wanhua Chemical Group Co., Ltd. |
Shandong |
N/A |
CN |
|
|
Assignee: |
Wanhua Chemical Group Co., Ltd.
(N/A)
|
Family
ID: |
1000005645872 |
Appl.
No.: |
16/323,671 |
Filed: |
August 24, 2016 |
PCT
Filed: |
August 24, 2016 |
PCT No.: |
PCT/CN2016/096531 |
371(c)(1),(2),(4) Date: |
February 06, 2019 |
PCT
Pub. No.: |
WO2018/032522 |
PCT
Pub. Date: |
February 22, 2018 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20190201878 A1 |
Jul 4, 2019 |
|
Foreign Application Priority Data
|
|
|
|
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Aug 18, 2016 [CN] |
|
|
201610700895.9 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J
21/04 (20130101); C07C 213/02 (20130101); B01J
37/0213 (20130101); C08G 65/325 (20130101); C08G
65/33306 (20130101); B01J 23/46 (20130101); B01J
23/8946 (20130101); B01J 37/035 (20130101); B01J
23/8966 (20130101); B01J 23/44 (20130101); B01J
37/0236 (20130101); C08G 65/3255 (20130101); B01J
23/8926 (20130101); B01J 37/18 (20130101); B01J
23/56 (20130101); B01J 37/08 (20130101); B01J
23/8993 (20130101) |
Current International
Class: |
B01J
21/04 (20060101); B01J 23/44 (20060101); B01J
23/56 (20060101); B01J 23/89 (20060101); B01J
37/02 (20060101); B01J 37/03 (20060101); B01J
37/08 (20060101); B01J 37/18 (20060101); C07C
213/02 (20060101); C08G 65/325 (20060101); B01J
21/14 (20060101); B01J 21/12 (20060101); B01J
21/10 (20060101); B01J 21/08 (20060101); B01J
21/06 (20060101); C08G 65/333 (20060101); B01J
23/46 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1546550 |
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Nov 2004 |
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CN |
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101842345 |
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Sep 2010 |
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CN |
|
102336903 |
|
Feb 2012 |
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CN |
|
102875795 |
|
Jan 2013 |
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CN |
|
103709391 |
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Apr 2014 |
|
CN |
|
104383918 |
|
Mar 2015 |
|
CN |
|
105008431 |
|
Oct 2015 |
|
CN |
|
105399940 |
|
Mar 2016 |
|
CN |
|
12008.3 |
|
Oct 1918 |
|
GB |
|
2015069531 |
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May 2015 |
|
WO |
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Other References
International Search Report PCT/CN2016/096531 dated Apr. 12, 2017.
cited by applicant .
Database WPI Week 201640 Thomson Scientific, London, GB; AN
2016-184704 -& CN 105 399 940 A (Wanhua Chem Group Co LTO) Mar.
16, 2016 (Mar. 16, 2016). cited by applicant .
Extended European Search Report for Application No. 16913278.4
dated Feb. 28, 2020, 9 pages. cited by applicant.
|
Primary Examiner: Nguyen; Cam N.
Attorney, Agent or Firm: Lerner, David, Littenberg, Krumholz
& Mentlik, LLP
Claims
The invention claimed is:
1. A supported catalyst used for synthesizing polyether amines,
comprising a support and active components, wherein the active
components comprises: 1-15 wt % of Ni, 0.5-10 wt % of Cu, 0.1-1.0
wt % of Pd, and 0.05-0.5 wt % of Rh, based on the total weight of
the catalyst.
2. The supported catalyst according to claim 1, wherein the active
components of the catalyst comprises: 4-12 wt % of Ni, 1-8 wt % of
Cu, 0.5-0.8 wt % of Pd, and 0.15-0.4 wt % Rh, based on the total
weight of the catalyst.
3. The supported catalyst according to claim 2, wherein the active
components of the catalyst comprises: 5-10 wt % of Ni, 3-5 wt % of
Cu, 0.6-0.7 wt % of Pd, and 0.2-0.3 wt % of Rh, based on the total
weight of the catalyst.
4. The supported catalyst according to claim 2, wherein the
catalyst optionally comprises an auxiliary agent which is selected
from the group consisting of Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La,
Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge, and any combination
thereof, preferably the group consisting of Zr, Ce, Mg, Mo, Ti, and
any combination thereof, more preferably Zr and/or Mg.
5. The supported catalyst according to claim 1, wherein the
catalyst optionally comprises an auxiliary agent which is selected
from the group consisting of Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La,
Hf, Sr, Sb, Mg, Be, Re, Ta, Ti, Sc, Ge, and any combination
thereof, preferably the group consisting of Zr, Ce, Mg, Mo, Ti, and
any combination thereof, more preferably Zr and/or Mg.
6. The supported catalyst according to claim 5, wherein the content
of the auxiliary agent is 0-0.5 wt %, preferably 0.05-0.45 wt %,
more preferably 0.1-0.3 wt %, based on the total weight of the
catalyst.
7. The supported catalyst according to claim 5, wherein the total
content of the active components is not less than 5 wt %,
preferably not less than 10 wt %, based on the total weight of the
catalyst.
8. The supported catalyst according to claim 5, wherein the support
is selected from the group consisting of porous
.gamma.-Al.sub.2O.sub.3, SiO.sub.2, MgO, TiO.sub.2, ZrO.sub.2, and
any combination thereof, preferably .gamma.-Al.sub.2O.sub.3.
9. The supported catalyst according to claim 1, wherein the total
content of the active components is not less than 5 wt %,
preferably not less than 10 wt %, based on the total weight of the
catalyst.
10. The supported catalyst according to claim 1, wherein the
support is selected from the group consisting of porous
.gamma.-Al.sub.2O.sub.3, SiO.sub.2, MgO, TiO.sub.2, ZrO.sub.2, and
any combination thereof, preferably .gamma.-Al.sub.2O.sub.3.
11. A method of preparing the supported catalyst according to claim
1, wherein the method comprises the following steps: 1) Preparation
of a metal salt solution: weighing metal salts proportionally, and
adding deionized water to prepare a metal salt solution; wherein
the metal salts are metal salts of the active components and the
optional auxiliary agent; 2) Adsorption: adding the support to
adsorb the metal salt complex solution obtained in step 1) to
obtain an adsorbed wet support; 3) Drying, calcining, and reducing
the wet support to obtain the supported catalyst.
12. The method according to claim 11, wherein the metal salt is one
or more of metal halide, metal nitrate, organic acid metal salt,
preferably one or more of metal nitrate, metal formate, metal
acetate and metal oxalate, more preferably metal nitrate.
13. The method according to claim 12, wherein the method further
comprises step 1a) preparation of a metal salt complex solution:
forming a metal salt complex solution by reacting the metal salt
solution with a ligand; preferably, the ligand is one or more of
ammonia and organic amines, more preferably one or more of ammonia,
EDTA and diethylamine.
14. The method according to claim 11, wherein the method further
comprises step 1a) preparation of a metal salt complex solution:
forming a metal salt complex solution by reacting the metal salt
solution with a ligand; preferably, the ligand is one or more of
ammonia and organic amines, more preferably one or more of ammonia,
EDTA and diethylamine.
15. The method according to claim 14, wherein the method further
comprises step 2a) in-situ precipitation of CO.sub.2: precipitating
the metal salt complex on the adsorbed wet support obtained in the
step 2) by using carbon dioxide gas; preferably, the reaction
condition for in-situ precipitation of CO.sub.2 is: performing the
precipitation reaction in an atmosphere containing carbon dioxide
at a reaction temperature of 20.degree. C.-50.degree. C.,
preferably 30.degree. C.-40.degree. C. for 2 h-10 h, preferably 4
h-6 h.
16. A method for preparing a polyether amine by amination of a
polyether polyol, wherein the method is as follow: subjecting the
polyether polyol to a reductive amination reaction in the presence
of hydrogen, an amination reagent and a supported catalyst to
prepare a polyether amine; wherein the supported catalyst is
prepared by the method according to claim 11.
17. A method for preparing a polyether amine by amination of a
polyether polyol, wherein the method is as follow: subjecting the
polyether polyol to a reductive amination reaction in the presence
of hydrogen, an amination reagent and a supported catalyst to
prepare a polyether amine; wherein the supported catalyst is the
supported catalyst according to claim 1.
18. The method according to claim 17, wherein the polyether polyol
contains an EO and/or PO skeleton and has a weight average
molecular weight of 90-7,000, preferably a molecular weight of
100-5,000, more preferably a molecular weight of 200-600.
19. The method for preparing a polyether amine by amination of a
polyether polyol according to claim 18, wherein the space velocity
of the polyether polyol is 0.01-3 h.sup.-1, preferably 0.1-1.0
h.sup.-1.
20. The method according to claim 17, wherein the space velocity of
the polyether polyol is 0.01-3 h.sup.-1, preferably 0.1-1.0
h.sup.-1.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a national phase entry under 35 U.S.C.
.sctn. 371 of International Application No. PCT/CN2016/096531,
filed Aug. 24, 2016, which claims priority from Chinese Patent
Application No. 201610700895.9 filed Aug. 18, 2016, all of which
are hereby incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a supported catalyst used for
synthesizing a polyether amine, a preparation method thereof and a
method for preparing a polyether amine by amination of a polyether
polyol, and belongs to the field of polymer synthesis.
BACKGROUND OF ART
Polyether amine, also known as Amino-Terminated Polyether (ATPE),
is a type of polyoxyalkylene compound in which the molecular main
chain is a polyether skeleton and the terminals are terminated by
amino. Most of these ATPEs are obtained by using polyether
(polyethylene glycol, polyoxypropylene ether, etc.) as the reaction
raw material and converting the terminal hydroxyls of polyether
polyol into corresponding amine groups or amino groups (the
terminal group is usually a primary amine, a secondary amine or a
polyamine containing active hydrogen) by employing different
chemical treatment methods. At present, only Huntsman and BASF have
industrialized amino-terminated polyether amines around the
world.
Due to the reactivity of amine groups or amino groups at the
terminal ends of the polyether skeleton, polyether amine can
interact with a variety of reactive groups, such as epoxy groups
and isocyanate groups; in addition, due to the presence of ether
linkages in the polyether chain, polyether amine can also dissolve
easily in a variety of organic substances, which greatly expands
the application range of polyether amines in the industrial field.
Therefore, polyether amines are widely used in the fields of epoxy
resin curing agents, polyurethane (polyurea) industries, and
gasoline detergent dispersants because of their superior
properties.
The methods for synthesizing polyether amines mainly include
reductive amination method, leaving group method and polyether
nitrile reduction method. Wherein, the reductive amination method
is also called as hydroamination method, and since its process
route is the most advanced, the quality of the products is the most
stable and it is also more environmentally friendly, the reductive
amination method has become the main method for industrial
production of polyether amines at home and abroad.
The key to this production process is the choice and preparation of
the catalyst. Catalysts suitable for reductive amination contain
metals such as Ni, Co and Cu as active components, which sometimes
are referred to as hydrogenation/dehydrogenation catalysts, because
they are active in these two types of reactions. Other elements in
the periodic table are also often introduced into the catalyst to
give it the best activity or selectivity.
U.S. Pat. No. 3,654,370 discloses a process for the catalytic
amination of a polyether diol having a molecular weight of 1000 and
a polyether triol having a molecular weight of 1500 using a
continuous tubular reactor, and the catalyst thereof is prepared by
a coprecipitation method and contains 75% of Ni, 23% of Cu and 2%
of Cr. The catalyst has the problems of complicated preparation
process, poor strength and fragility.
U.S. Pat. No. 4,766,245 discloses a Raney nickel catalyst for the
amination of polyether polyols. The catalyst comprises 60-75% of Ni
and 40-25% of Al, but the catalyst is only suitable for the
amination reaction of polyether polyols having molecular weight of
more than 500.
U.S. Pat. No. 4,014,933 discloses an alumina or silica supported
Co--Ni--Cu catalyst and a process for the amination of
polypropylene glycol. The catalyst comprises 10% of Co, 10% of Ni,
4% of Cu, and 0.4% of phosphoric acid, and the rest is
Al.sub.2O.sub.3. The catalyst is suitable for the amination
reaction of polyether polyols having molecular weight of more than
1400.
U.S. Pat. Nos. 4,152,353 and 4,153,581 disclose a catalyst of
alumina supported Ni, Cu and auxiliary agent selected from one or
two metals of Fe and Zn. The catalyst comprises 30% of Ni (or 30%
of Co), 63% of Cu and 7% of Fe and/or Zn, and the rest is
Al.sub.2O.sub.3. The catalyst has the problems of low activity and
poor selectivity.
U.S. Pat. No. 4,209,424 discloses an alumina supported transition
metal amination catalyst, and uses it for the amination of a
polyether polyol. The catalyst comprises at least one or two of Ni,
Co and Cu, wherein the metal content is 30-70%, the rest is
Al.sub.2O.sub.3.
U.S. Pat. No. 4,973,761 discloses an amination catalyst of alumina
supported Ni, Co and Cu, and uses it for the amination of
polytetrahydrofuran ether glycol. The catalyst is suitable for
amination of polyether polyols having molecular weight of 640 to
4000, but has problems of low catalyst activity and poor product
selectivity.
U.S. Pat. No. 5,003,107 discloses an amination catalyst of alumina
supported Ni, Co, Cr, and Mo, and uses it for the amination of
polyoxytetramethylene glycol. The catalyst comprises 70-75% of Ni,
20-25% of Cu, 0.5-5% of Cr and 1-5% of Mo, and the rest is
Al.sub.2O.sub.3. In the amination process of polytetrahydrofuran
polyether with molecular weight of 1000-2000 using a continuous
tubular reactor, the conversion rate of raw materials is 91-96%,
and the product selectivity is 92-97%. The catalyst does not
involve the amination of polyether polyols having a molecular
weight of less than 500.
US20100069671 employs metals of at least 80 wt % of Co and Al, less
than 5 wt % of Cu as a catalyst to catalyze the corresponding
polyether polyol to prepare polyether amine, the catalyst is
suitable for polyether polyols having molecular weight of more than
2000, and cannot be used for the amination of polyether polyols
having molecular weight of less than 500.
CN1546550A discloses a process for the preparation of polyether
amine by hydroamination of a polyfunctional amine having a
molecular weight of 2000 and a trifunctional polyether having a
molecular weight of 5000. Of which a skeleton nickel catalyst with
60-80 wt % of Ni, 10-35 wt % of Al, and 2-10 wt % of Cr is used.
The catalyst is not suitable for the polyether amine preparation
process by amination of polyether polyols containing various
monomer skeletons such as ethylene oxide (EO) and/or propylene
oxide (PO) and polyether polyols having average molecular weight of
less than 500.
CN102336903A discloses an amination process of polyether polyols
having molecular weight of more than 100, of which a skeleton
nickel catalyst having a Ni content of 85-95 wt % and an Al content
of 5-15 wt % is used. The catalyst has a higher activity for the
amination of the polyether polyols having molecular weight of more
than 1000, and for the amination of the polyether polyols having
molecular weight of less than 500, the conversion of the raw
material is 80-90%, and the selectivity of the product is
90-95%.
The above-mentioned catalysts of prior art encounter the problems
of complicated preparation processes, fragility, high metal content
and poor economy. At the same time, the catalysts of prior art are
only suitable for the amination of polyether polyols with large
molecular weight, while exhibiting poor activity and selectivity
for the amination reaction of low molecular weight polyether
polyols, especially polyether polyols having average molecular
weight of less than 500.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a supported
catalyst for synthesizing a polyether amine, a preparation method
thereof, and a method for preparing a polyether amine by amination
of a polyether polyol. The catalyst can be used for catalyzing the
amination reaction of a polyether polyol and has extremely high
activity and selectivity.
In order to achieve one aspect of the above object, the technical
solution adopted by the present invention of the supported catalyst
for synthesizing a polyether amine is as follows:
A supported catalyst for synthesizing a polyether amine, wherein
the catalyst comprises a support and active components, the active
components comprise Ni, Cu, Pd and Rh, and each has a content as
follows based on the total weight of the catalyst:
the content of Ni element is 1-15 wt %, preferably 4-12 wt %, more
preferably 5-10 wt %;
the content of Cu element is 0.5-10 wt %, preferably 1-8 wt %, more
preferably 3-5 wt %;
the content of Pd element is 0.1-1.0 wt %, preferably 0.5-0.8 wt %,
more preferably 0.6-0.7 wt %;
the content of Rh element is 0.05-0.5 wt %, preferably 0.15-0.4 wt
%, more preferably 0.2-0.3 wt %.
The catalyst of the present invention optionally further comprises
an auxiliary agent which is selected from the group consisting of
Zr, Cr, Mo, Fe, Zn, Sn, Bi, Ce, La, Hf, Sr, Sb, Mg, Be, Re, Ta, Ti,
Sc, Ge and any combination thereof, preferably the group consisting
of Zr, Ce, Mg, Mo, Ti, and any combination thereof, and more
preferably Zr and/or Mg.
In a preferred embodiment of the present invention, the catalyst
consists of a support, active components and an optional auxiliary
agent. In the present invention, it should be noted that "optional"
means things may or may not exist.
The content of the auxiliary agent is preferably 0-0.5 wt %,
further preferably 0.05-0.45 wt %, more preferably 0.1-0.3 wt %
based on the total weight of the catalyst to further enhance the
catalytic effect thereof. In the present invention, when the
content of a certain component is 0%, it means that this component
is not contained.
The total content of the active components is preferably not less
than 5 wt %, further preferably not less than 10%, more preferably
not less than 12 wt %, such as 11 wt %, 14 wt %, 16 wt %, 18 wt %
or 20 wt %, based on the total weight of the catalyst, to further
enhance the catalytic effect thereof. Of course, those skilled in
the art will understand that excessively high content of active
components will further increase the catalyst cost. In a preferred
embodiment, the active components consist of Ni, Cu, Pd and Rh.
In the present invention, the support may be a porous oxide such as
one or more of the group consisting of .gamma.-Al.sub.2O.sub.3,
SiO.sub.2, MgO, TiO.sub.2 and ZrO.sub.2, preferably
.gamma.-Al.sub.2O.sub.3. The preparation method of the above porous
oxides is well known in the art. For example, as to
.gamma.-Al.sub.2O.sub.3, Al.sub.2(SO.sub.4).sub.3 is formulated
into a 6 wt % aqueous solution, and 20 wt % of NH.sub.3.H.sub.2O is
added, the reaction is kept for 1 h under strong stirring to obtain
Al(OH).sub.3 precipitate. And then the aluminum hydroxide product
is obtained by filtration, water washing and drying, which is
molded by band extrusion and activated by calcination at
550.degree. C. for 4 h to obtain the .gamma.-Al.sub.2O.sub.3.
Preferably the .gamma.-Al.sub.2O.sub.3 has the following
properties: specific surface area: 180-220 m.sup.2/g, pore volume:
0.9-1.2 ml/g, pore diameter: 9-12 nm, mechanical strength: >50
N/cm, bulk density: 0.60-0.80 g/ml.
The support of the present invention may be in a variety of shapes,
and the specific shape of the support may be designed and selected
according to the reactors for catalyzing different polyether
polyols and amination reagents (for example, it may be a
kettle-type reactor, a fixed bed reactor, a fluidized bed reactor,
a tubular-type reactor or a bubble tower reactor according to
actual needs), including but not limited to one or more of sheet,
strip and clover type.
The catalyst according to the present invention is suitable for the
amination reaction of polyether polyols having weight average
molecular weight of 90-7,000, preferably 100-5,000, more preferably
200-600, for example 300, 400 or 500.
In the art of the present invention, primary amines are usually
prepared by reacting polyether polyols with ammonia under reductive
amination process conditions. The reaction mechanism is generally
considered to include that: in the presence of a catalyst, a
hydroxyl is dehydrogenated to form a carbonyl, the carbonyl is
aminated and dehydrated to form an olefinimine, and the olefinimine
is reduced and converted to a terminal amino by hydrogenation
catalysts. Research has found that a good selectivity to primary
amines is generally achieved when ammonia is in excess and a
secondary alcohol is used in the reaction under appropriate
catalytic reaction conditions. However, under the same catalytic
reaction conditions, when a primary alcohol is used as reactant,
not only the selectivity of the primary amine in the reaction
product is low, but also a significantly higher secondary amine
product and significantly higher undesired "hydrogenolysis"
by-products are favored. In particular, the hydrogenolysis
by-products are formed by reductive decomposition or by formal
addition of hydrogen to C--C, C--O and C--N bonds when the alcohol
conversion rate is high.
In accordance with the present invention, we have surprisingly
found that the synergistic effect generated by the specific
combination of the active components of nickel, copper, palladium
and rhodium in the catalyst can greatly reduce by-products (eg,
monoamino and/or biamino by-products, dimethylmorpholine
by-products generated by low molecular weight polyethers, etc.) in
the amination process of polyether polyols, especially under the
condition that the polyether polyol is completely converted, and
thereby the selectivity and product yield of the primary amine are
greatly improved. At the same time, due to the decrease of
by-products, the viscosity of the product is lower, the color is
lighter (i.e., the color number is smaller), and the additional
value is higher.
In order to achieve another aspect of the above object, the method
for preparing the supported catalyst provided by the present
invention adopts the following technical solution:
A preparation method for a supported catalyst for synthesizing
polyetheramines, comprising the following steps:
1) Preparation of a metal salt solution: weighing metal salts
proportionally, and adding deionized water, alcohol or ketone
solvents to prepare a metal salt solution; wherein the metal salts
are the metal salts of the active components and the optional
auxiliary agent;
2) Adsorption: using the support to adsorb the metal salt solution
obtained in step 1) to obtain an adsorbed wet support;
3) Drying, calcining and reducing the wet support to obtain the
supported catalyst.
In the step 1), the metal salts in the metal salt solution include
but is not limited to one or more of metal halide, metal nitrate,
organic acid metal salt, and the like, preferably one or more of
metal nitrate, metal formate, metal acetate and metal oxalate, more
preferably metal nitrate.
The ratio of the amount of each metal element in the metal salts
can be determined according to the ratio of each active component
and each component of the auxiliary agent in the foregoing
catalyst, wherein the metal salt solution is an aqueous solution in
which the metal salts are dissolved in water to form the metal salt
solution, and the concentration thereof may be 5-60 wt %, such as
20 wt %, 30 wt % or 40 wt %.
In the step 2), the method for adsorbing the metal salt solution
with the support is well known in the art, for example, the support
may be impregnated with the metal salt solution obtained in the
step 1), or the metal salt solution obtained in the step 1) may be
sprayed on the support, thereby a adsorbed wet support is obtained.
Those skilled in the art understand that the solution
concentration, the impregnating time or the spray amount can be
adjusted to adjust the adsorption amount of the metal salt in the
support, thereby controlling the content of the active components
or the auxiliary agent in the catalyst, and the adsorption process
can be conducted for one time or repeatedly. In one embodiment, the
volume ratio of the metal salt solution to the support can also be
controlled within a suitable range, so that the metal salt solution
can be substantially completely absorbed by the support or the
solid-liquid mixture of the obtained support and the solution can
be evaporated to remove excess solvent.
The impregnation process can be carried out in various ways, for
example, impregnating the support with a solution comprising
various metal salts, or mixing various metal salt solutions
uniformly and impregnating it onto the support, or impregnating the
support sequentially with different metal salt solutions; those
skilled in the art understand that the impregnation process and the
spraying process can be done in one step or in multiple steps.
In the step 3), a catalyst precursor is obtained firstly by giving
drying and calcination treatment to the obtained support. The above
treating processes are common in the art, wherein the drying
condition may be: the drying temperature is 50.degree.
C.-120.degree. C., preferably 60.degree. C.-90.degree. C.; the
drying time is 4 h-24 h, preferably 8-12 h; and the calcination
condition may be: the calcination temperature is 200.degree.
C.-600.degree. C., preferably 300.degree. C.-500.degree. C.; the
calcination time is 2 h-12 h, preferably 4 h-8 h.
The catalyst precursor obtained by drying and calcination
treatments in the step 3) is subjected to reduction treatment after
cooling to obtain the supported catalyst of the present invention,
which can be used for the amination reaction of a polyether polyol,
and the above reduction treating process is a common process in the
art, for example, the catalyst precursor is subjected to reduction
at a temperature of 100.degree. C.-400.degree. C., preferably
200.degree. C.-300.degree. C.; the reduction process is carried out
in the presence of a gas containing hydrogen, wherein the reduction
time is 1 h-24 h, preferably 4 h-16 h. The reduction process uses a
gas containing hydrogen, such as pure hydrogen or a mixture of
inert gas and hydrogen, the inert gas including but not limited to
nitrogen, helium, neon, argon or krypton, preferably nitrogen;
preferably, the volume content of the inert gas is 5%-95%, more
preferably 50%-95% based on the total volume of the inert gas and
hydrogen.
According to the preparation method of the present invention, in a
preferred embodiment, the preparation method further comprises step
1a) preparation of a metal salt complex solution: forming a metal
salt complex solution by reacting the metal salt solution with a
ligand, and then performing step 2); That is, the metal salt
solution obtained in the step 1) is further prepared into a metal
salt complex solution instead of the metal salt solution itself to
perform the treatment of step 2).
In step 1a), the ligand comprises an inorganic ligand and/or an
organic ligand, and preferably is one or more of ammonia and
organic amines, more preferably is one or more of ammonia,
ethylenediaminetetraacetic acid (EDTA) and diethylamine, and
further preferably is ammonia. The molar ratio of the metal element
to the ligand in the metal salt complex solution is preferably
1:1-1:10, such as 1:3, 1:5 or 1:7.
According to the preparation method of the present invention, in a
preferred embodiment, the preparation method further comprises step
2a) in-situ precipitation of CO.sub.2: precipitating the metal salt
complex on the adsorbed wet support obtained in step 2) by using
carbon dioxide gas. That is, the adsorbed wet support obtained in
step 2) is subjected to the treatment in the step 3) after the
treatment in step 2a).
In step 2a), precipitating the metal salt complex (such as
carbonate precipitation) on the adsorbed wet support by using
carbon dioxide gas, and its reaction principle is well known in the
art. The specific reaction can be carried out in a tubular reactor,
wherein the gas containing carbon dioxide is introduced from one
end of the reactor and vented from the other end, so that the gas
can react with the metal salt complex on the support. The inlet
speed of the gas can be determined by a person skilled in the art
according to actual conditions, which will not be explored herein.
In the present invention, the reaction condition for in-situ
precipitation of CO.sub.2 may be: performing the precipitation
reaction in an atmosphere containing carbon dioxide at a reaction
temperature of 20-50.degree. C., preferably 30-40.degree. C. for
2-10 h, preferably 4-6 h. In order to keep the precipitation
reaction performing smoothly, the volume of carbon dioxide in the
gas should be enough to sufficiently precipitate the adsorbed wet
support in a controllable time, for example, the volume content of
carbon dioxide in the gas is not less than 20 vol %, such as 50 vol
% or 80 vol %. In addition, in order to accelerate the
precipitation reaction, the reaction can also be carried out under
a pressurized condition.
In order to achieve a further aspect of the above object, the
method for preparing a polyether amine by amination of a polyether
polyol provided by the present invention adopts the following
technical solutions:
A method for preparing a polyether amine by amination of a
polyether polyol, which is: subjecting the polyether polyol to a
reductive amination reaction in the presence of hydrogen, an
amination reagent and the supported catalyst of the present
invention to prepare the polyether amine.
The catalyst of the present invention is particularly suitable for
the reductive amination reaction of a polyol with polyether as
skeleton unit; said polyether polyol preferably contains an
ethylene oxide (EO) and/or propylene oxide (PO) skeleton, and has a
weight average molecular weight of 90-7,000, preferably 100-5,000,
more preferably 200-600, for example 300, 400 or 500; said
polyether polyol contains more than two hydroxyls.
Those skilled in the art understand that the expression "contain an
ethylene oxide (EO) and/or propylene oxide (PO) skeleton" means
that the polyether polyol is prepared by using one or more of
ethylene glycol, propylene glycol, trimethylolpropane (TMP) and
neopentyl glycol (NPG) as initiator to react with PO and/or EO, and
its specific preparation method is well known in the art and can
make a specific reference to Chinese invention patents
CN201210393578.9 and CN201310627712.1.
In the method for preparing a polyether amine according to the
present invention, the animation reagent is an organic amine having
C atoms no more than 10 and/or ammonia, and has the formula of
NHR.sub.1R.sub.2, wherein R.sub.1 and R.sub.2 may be the same or
different and are independently selected from the group consisting
of hydrogen, methyl, ethyl, propyl and isopropyl, preferably the
amination reagent is one or more of ammonia, methylamine and
dimethylamine.
The process for preparing polyether amines of the present invention
may be carried out intermittently or continuously, preferably
continuously. The preparation of the polyether amines by a
continuous process can be carried out in a tubular reactor in the
form of liquid phase reaction or gas phase reaction.
In the present invention, preferably, the molar ratio of the
animation reagent to the polyether polyol is (1-60):1, preferably
(6-20):1, such as 10:1, 14:1 or 16:1. The molar ratio of hydrogen
to polyether polyol is (0.01-1):1, preferably (0.05-0.5):1, such as
0.08:1, 0.1:1, 0.3:1 or 0.4:1.
Preferably, the space velocity of the polyether polyol is 0.01-3
h.sup.-1, preferably 0.1-1.0 h.sup.-1.
The reaction temperature of the reductive amination reaction of the
present invention may be 100-300.degree. C., preferably
150-250.degree. C., particularly preferably 180-230.degree. C.; and
the reaction pressure (absolute pressure) may be 1-30 MPa,
preferably 5-20 MPa, particularly preferably 10-18 MPa.
The reductive amination reaction of the present invention may or
may not use a solvent, and the solvent may be selected from one or
more of alcohols, ethers, and hydrocarbon compounds. Preferably the
solvent includes but not limited to one or more of water, methanol,
ethanol, benzene, cyclohexane, toluene, diethyl ether, THF, and
MTBE (methyl tert-butyl ether). The reductive amination reaction of
the present invention is preferably carried out without using a
solvent.
The catalyst prepared according to the present invention can make
the conversion rate of the raw material reach to about 100%, such
as more than 99.9%, the selectivity of the polyether amine product
reach to more than 99.0%, the product yield reach to more than
99.5%, and the content by-products reach to less than 0.5 wt %.
The beneficial effects of the present invention are:
(1) The active components Ni, Cu, Pd and Rh are introduced into the
polyether catalyst, and the synergistic effect produced by the
specific combination of Ni, Cu, Pd and Rh greatly reduces the
content of by-products (including monoamino and/or diamino
by-products, dimethylmorpholine by-products generated by low
molecular weight polyethers, etc.) in the amination process,
especially under the condition that the polyether is converted
completely, thereby greatly improving the selectivity and yield of
polyether amine products.
(2) The catalyst of the present invention is not only suitable for
the amination reaction of polyether polyols with large molecular
weight, but also particularly suitable for the amination reaction
of polyether polyols with low molecular weight (less than 500). The
catalyst exhibits extremely high activity and selectivity in the
amination reaction of polyether polyols with molecular weight of
less than 500.
(3) The sintering resistance and stability of the catalyst of the
present invention can be significantly improved by adding auxiliary
agent elements.
(4) In the preparation process of the catalyst, it is preferred to
use a metal salt complex solution such as a metal ammonium salt
solution to impregnate the support, and compared with using a
conventional metal salt aqueous solution (such as nitrate) or a
metal molten salt solution to impregnate the support, the metal
salt complex solution has a characteristic of low viscosity which
is favorable for the sufficient absorption of the support, thereby
improving the activity of the catalyst; at the same time, the metal
salt complex solution has the advantages of: low corrosivity, easy
to storage and transport, and economical to treat;
In addition, compared with drying the absorbed support directly or
using other conventional precipitating agents (such as sodium
carbonate or sodium hydroxide), the present invention preferably
uses carbon dioxide to in-situ precipitate the metal salt complex
on the support, which is beneficial to increase the activity of the
catalyst. Since carbon dioxide can easily enters the internal pores
of the support, it is advantageous for sufficient precipitation of
the metal salt complex solution such as metal ammonium salt, and
facilitates uniform distribution of the precipitation; in addition,
compared with conventional precipitants (such as sodium carbonate
or sodium hydroxide), the present invention avoids the step of
washing away the soluble salt adsorbed on the surface of the
support after precipitation by a large amount of water, and the
soluble salt produced in the present method can be removed merely
by heating volatilization or decomposition.
(5) The catalyst of the present invention has low metal load, good
dispersibility, high mechanical strength and lower cost, and has a
good application prospect.
EMBODIMENTS
The invention is further described in detail below by way of
specific examples, but it should not be understood that the scope
of the invention is limited to the following examples. Various
substitutions and modifications may be made without departing from
the spirit and scope of the invention.
Gas chromatograph: Shimadzu GC-2014 (FID) detector, SE-30 capillary
column (.phi.0.30 mm.times.30 m), injection port 270.degree. C.,
detector 270.degree. C.; temperature program: a constant
temperature of 70.degree. C. is kept for 1 min, then increased to
240.degree. C. at a rate of 40.degree. C./min, kept for 5 min.
Method for determination of hydroxyl value: see GB/T
12008.3-2009.
Method for determination of total amine value: the product is
titrated with a 0.5 mol/L hydrochloric acid solution, and the total
amine value of the product can be calculated by the mass of
hydrochloric acid consumed.
Raw material conversion rate: total amine value of the
product/total hydroxyl value of the raw material.times.100%.
Product yield: mass of polyether amine product/mass of polyether
polyol raw material.times.100%.
The reductive amination reactor in the Examples is a fixed bed
reactor.
Methylamine, dimethylamine, polyether polyols (PPG-230, T-2000,
D-5000, T-403): Wanhua Chemical Group Co., Ltd.
The reagents used below are analytically pure if not explicitly
stated.
In the following Examples, the support alumina used is WFC-05 type
.gamma.-alumina purchased from Zibo Wufeng Aluminum Magnesium
Technology Co., Ltd.
EXAMPLE 1
Into 85 ml of formate solution containing 6.5 g of Ni, 7.5 g of Cu,
0.9 g of Pd and 0.2 g of Rh (based on the weight of the metal
elements, the same as follows), ammonia water with a concentration
of 25 wt % was added dropwise until the precipitate formed was
completely dissolved, to obtain a mixed solution of metal ammonium
salts. At room temperature, 84.9 g of dried strip-shaped alumina
having a diameter of 3 mm was completely impregnated in the above
solution, and the solution was allowed to stand for 5.5 hours and
substantially completely adsorbed.
The impregnated support was taken out and placed in a tubular
reactor, and was treated with carbon dioxide gas introduced at
45.degree. C. for 4 hours, which was then slowly heated to
80.degree. C. to dry for 12 hours.
Nitrogen gas was introduced to completely replace carbon dioxide in
the tubular reactor, and part of the support was calcined at
450.degree. C. for 4.5 h in nitrogen atmosphere. An excess barium
hydroxide solution was used to absorb the CO.sub.2 produced by the
decomposition of the carbonate, so that the carbon dioxide was
completely converted into barium carbonate precipitate, and 2 drops
of phenolphthalein indicator was added into the solution which was
then titrated with an oxalic acid standard solution having a
concentration of c (mol/ml) until the color of the solution changed
from red to colorless, while the volume a (ml) of the consumed
oxalic acid standard solution was recorded. At the same time, the
barium hydroxide solution without absorbing any CO.sub.2 was used
as a blank titration to record the volume b (ml) of the consumed
oxalic acid standard solution. The mass of CO.sub.2 produced after
calcination of the catalyst can be calculated according to the
following formula. m=M*(b-a)*c
Wherein, m is the mass of carbon dioxide, g; M is the molecular
weight of carbon dioxide, g/mol; a is the volume of the oxalic acid
standard solution for sample titration, ml; b is the volume of the
oxalic acid standard solution for blank titration, ml; c is the
molar concentration of the oxalic acid standard solution,
mol/ml.
After calculation, the carbon dioxide produced by the decomposition
of carbonate is about 96% of the theoretical consumption of carbon
dioxide, indicating that the metal salt has been sufficiently
precipitated in the in-situ precipitation step of carbon
dioxide.
The remaining support was reduced with a mixture of 5 vol % of
hydrogen and 95 vol % of nitrogen at 200.degree. C. for 12 h to
obtain a supported catalyst A-1 containing 6.5 wt % of Ni, 7.5 wt %
of Cu, 0.9 wt % of Pd and 0.2 wt % of Rh.
EXAMPLE 2
Into 86 ml of nitrate solution containing 10.0 g of Ni, 3.0 g of
Cu, 0.5 g of Pd, 0.3 g of Rh and 0.1 g of Zr, ammonia water with a
concentration of 25 wt % was added dropwise until the precipitate
formed was completely dissolved to obtain a mixed solution of metal
ammonium salts. At room temperature, 86.1 g of dried strip-shaped
alumina having a diameter of 3 mm was completely impregnated in the
above solution, and the solution was allowed to stand for 6 hours
and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 35.degree. C., and was treated with the introduced carbon
dioxide for 6 h, which was then slowly heated to 80.degree. C. to
dry for 10 h, calcined at 400.degree. C. for 4 h, cooled, and then
reduced at 250.degree. C. with a mixed gas of 50 vol % of hydrogen
and 50 vol % of nitrogen for 8 hours to obtain a supported catalyst
A-2 containing 10.0 wt % of Ni, 3.0 wt % of Cu, 0.5 wt % of Pd, 0.3
wt % of Rh and 0.1 wt % of Zr.
EXAMPLE 3
Into 86 ml of nitrate solution containing 8.5 g of Ni, 4.5 g of Cu,
0.65 g of Pd, 0.5 g of Rh and 0.45 g of Mg, ammonia water with a
concentration of 28 wt % was added dropwise until the precipitate
formed was completely dissolved to obtain a mixed solution of metal
ammonium salts. At room temperature, 85.4 g of dried spherical
alumina having a diameter of 3 mm was completely impregnated in the
above solution, and the solution was allowed to stand for 8 hours
and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 40.degree. C., and was treated with the introduced carbon
dioxide for 5 h, which was then slowly heated to 85.degree. C. to
dry for 8 h, calcined at 450.degree. C. for 3 h, cooled, and then
reduced at 100.degree. C. with a mixed gas of 20 vol % of hydrogen
and 80 vol % of nitrogen for 16 hours to obtain a supported
catalyst A-3 containing 8.5 wt % of Ni, 4.5 wt % of Cu, 0.65 wt %
of Pd, 0.5 wt % of Rh and 0.45 wt % of Mg.
EXAMPLE 4
Into 84 ml of acetate solution containing 9.5 g of Ni, 5.0 g of Cu,
0.7 g of Pd, 0.4 g of Rh, 0.25 g of Ce, 0.15 g of Mo, 0.05 g of Ti
and 0.05 g of Fe, ammonia water with a concentration of 30 wt % was
added dropwise until the precipitate formed was completely
dissolved to obtain a mixed solution of metal ammonium salts. At
room temperature, 83.9 g of dried clover-type alumina having a
diameter of 3 mm was completely impregnated in the above solution,
and the solution was allowed to stand for 5 hours, and the solution
was substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 30.degree. C., and was treated with the introduced carbon
dioxide for 4 h, which was then slowly heated to 90.degree. C. to
dry for 6 h, calcined at 300.degree. C. for 8 h, cooled, and then
reduced at 250.degree. C. with a mixed gas of 5 vol % of hydrogen
and 95 vol % of nitrogen for 24 hours to obtain a supported
catalyst A-4 containing 9.5 wt % of Ni, 5.0 wt % of Cu, 0.7 wt % of
Pd, 0.4 wt % of Rh, 0.24 wt % of Ce, 0.15 g of Mo, 0.05 g of Ti and
0.05 g of Fe.
EXAMPLE 5
Into 86 ml of nitrate solution containing 12.0 g of Ni, 1.0 g of
Cu, 0.8 g of Pd, 0.2 g of Rh, 0.1 g of Ce, 0.27 g of Mg, 0.03 g of
Zn, and 0.1 g of Sn, ammonia water with a concentration of 25 wt %
was added dropwise until the precipitate formed was completely
dissolved to obtain a mixed solution of metal ammonium salts. At
room temperature, 85.5 g of dried strip-shaped alumina having a
diameter of 2 mm was completely impregnated in the above solution,
and the solution was allowed to stand for 7 hours and substantially
completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 50.degree. C., and was treated with the introduced carbon
dioxide for 2 h, which was then slowly heated to 60.degree. C. to
dry for 12 h, calcined at 500.degree. C. for 2 h, cooled, and then
reduced at 300.degree. C. with pure hydrogen for 4 hours to obtain
a supported catalyst A-5 containing 12.0 wt % of Ni, 1.0 wt % of
Cu, 0.8 wt % of Pd, 0.2 wt % of Rh, 0.1 wt % of Ce, 0.27 wt % of
Mg, 0.03 wt % of Zn and 0.1 wt % of Sn.
EXAMPLE 6
Into 88 ml of oxalate solution containing 5.0 g of Ni, 5.5 g of Cu,
1.0 g of Pd, 0.3 g of Rh, 0.05 g of Zr, 0.3 g of Mg, 0.07 g of Zn,
0.05 g of Fe and 0.03 g of Sn, ammonia water with a concentration
of 25 wt % was added dropwise until the precipitate formed was
completely dissolved to obtain a mixed solution of metal ammonium
salts. At room temperature, 87.7 g of dried cylindrical alumina
having a diameter of 3 mm was completely impregnated in the above
solution, and the solution was allowed to stand for 6 hours and
substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 20.degree. C., and was treated with the introduced carbon
dioxide for 10 h, which was then slowly heated to 85.degree. C. to
dry for 10 h, calcined at 400.degree. C. for 4 h, cooled, and then
reduced at 240.degree. C. with pure hydrogen for 10 hours to obtain
a supported catalyst A-6 containing 5.0 wt % of Ni, 5.5 wt % of Cu,
1.0 wt % of Pd, 0.3 wt % of Rh, 0.05 wt % of Zr, 0.3 wt % of Mg,
0.07 wt % of Zn, 0.05 wt % of Fe and 0.03 wt % of Sn.
EXAMPLE 7
Into 87 ml of nitrate solution containing 4.0 g of Ni, 8.0 g of Cu,
0.6 g of Pd, 0.05 g of Rh, 0.1 g of Mg, 0.15 g of Ce, 0.08 g of Mo
and 0.12 g of Fe, ammonia water with a concentration of 28 wt % was
added dropwise until the precipitate formed was completely
dissolved to obtain a mixed solution of metal ammonium salts. At
room temperature, 86.9 g of dried strip-shaped alumina having a
diameter of 3 mm was completely impregnated in the above solution,
and the solution was allowed to stand for 6 hours and substantially
completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 35.degree. C., and was treated with the introduced carbon
dioxide for 7 h, slowly heated to 50.degree. C. and dried for 24 h,
calcined at 350.degree. C. for 6 h, cooled, and then reduced at
220.degree. C. with pure hydrogen for 10 hours to obtain a
supported catalyst A-7 containing 7.5 wt % of Ni, 8.0 wt % of Cu,
0.6 wt % of Pd, 0.1 wt % of Rh, 0.1 wt % of Mg, 0.15 wt % of Ce,
0.08 wt % of Mo and 0.12 wt % of Fe.
EXAMPLE 8
Into 88 ml of nitrate solution containing 1.0 g of Ni, 10.0 g of
Cu, 0.3 g of Pd, 0.15 g of Rh, 0.2 g of Zr, 0.04 g of Ce, 0.05 g of
Mo, 0.1 g of Ti and 0.06 g of Sn, ammonia water with a
concentration of 25 wt % was added dropwise until the precipitate
formed was completely dissolved to obtain a mixed solution of metal
ammonium salts. At room temperature, 88.1 g of dried spherical
alumina having a diameter of 2 mm was completely impregnated in the
above solution, and the solution was allowed to stand for 7 hours
and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 35.degree. C., and was treated with the introduced carbon
dioxide for 6 h, which was then slowly heated to 120.degree. C. to
dry for 4 h, calcined at 600.degree. C. for 5 h, cooled, and then
reduced at 400.degree. C. with pure hydrogen for 1 hours to obtain
a supported catalyst A-8 containing 1.0 wt % of Ni, 10.0 wt % of
Cu, 0.3 wt % of Pd, 0.15 wt % of Rh, 0.2 wt % of Zr, 0.04 wt % of
Ce, 0.05 wt % of Mo, 0.1 wt % of Ti and 0.06 wt % of Sn.
EXAMPLE 9
Into 84 ml of nitrate solution containing 15.0 g of Ni, 0.5 g of
Cu, 0.1 g of Pd, 0.25 g of Rh, 0.3 g of Zr and 0.05 g of Mg,
ammonia water with a concentration of 28 wt % was added dropwise
until the precipitate formed was completely dissolved to obtain a
mixed solution of metal ammonium salts. At room temperature, 83.8 g
of dried spherical alumina having a diameter of 3 mm was completely
impregnated in the above solution, and the solution was allowed to
stand for 6 hours and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 40.degree. C., and was treated with the introduced carbon
dioxide was introduced 8 h, which was then slowly heated to
85.degree. C. to dry for 6 h, calcined at 200.degree. C. for 12 h,
cooled, and then reduced at 240.degree. C. with a mixed gas of 10
vol % of hydrogen and 90 vol % of nitrogen for 12 hours to obtain a
supported catalyst A-9 containing 15 wt % of Ni, 0.5 wt % of Cu,
0.1 wt % of Pd, 0.25 wt % of Rh, 0.3 wt % of Zr and 0.05 wt % of
Mg.
EXAMPLE 10
Into 84 ml of nitrate solution containing 6.0 g of Ni, 9.5 g of Cu,
0.4 g of Pd, 0.35 g of Rh and 0.05 Mg, ammonia water with a
concentration of 25 wt % was added dropwise until the precipitate
formed was completely dissolved to obtain a mixed solution of metal
ammonium salts. At room temperature, 83.7 g of dried strip-shaped
alumina having a diameter of 3 mm was completely impregnated in the
above solution, and the solution was allowed to stand for 7 hours
and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 30.degree. C., and was treated with the introduced carbon
dioxide for 8 h, which was then slowly heated to 80.degree. C. to
dry for 6 h, calcined at 350.degree. C. for 10 h, cooled, and then
reduced at 200.degree. C. with a mixed gas of 25 vol % of hydrogen
and 75 vol % of nitrogen for 8 hours to obtain a supported catalyst
A-10 containing 6 wt % of Ni, 9.5 wt % of Cu, 0.4 wt % of Pd, 0.35
wt % of Rh and 0.05 wt % of Mg.
EXAMPLE 11
Into 86 ml of nitrate solution containing 7.0 g of Ni, 6.5 g of Cu,
0.75 g of Pd, 0.15 g of Rh, 0.15 g of Zr and 0.15 Mg, ammonia water
with a concentration of 25 wt % was added dropwise until the
precipitate formed was completely dissolved to obtain a mixed
solution of metal ammonium salts. At room temperature, 85.3 g of
dried clover-type alumina having a diameter of 3 mm was completely
impregnated in the above solution, and the solution was allowed to
stand for 5 hours and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 35.degree. C., and was treated with the introduced carbon
dioxide for 7 h, slowly heated to 85.degree. C. and dried for 6 h,
calcined at 450.degree. C. for 8 h, cooled, and then reduced at
300.degree. C. with pure hydrogen for 4 hours to obtain a supported
catalyst A-11 containing 7 wt % of Ni, 6.5 wt % of Cu, 0.75 wt % of
Pd, 0.15 wt % of Rh, 0.15 wt % of Zr and 0.15 wt % of Mg.
EXAMPLE 12
Into 85 ml of nitrate solution containing 8.0 g of Ni, 7.0 g of Cu,
0.25 g of Pd, 0.05 g of Rh, and 0.2 g of Zr, ammonia water with a
concentration of 25 wt % was added dropwise until the precipitate
formed was completely dissolved to obtain a mixed solution of metal
ammonium salts. At room temperature, 84.5 g of dried cylindrical
alumina having a diameter of 3 mm was completely impregnated in the
above solution, and the solution was allowed to stand for 6 hours
and substantially completely adsorbed.
The impregnated support was placed in a tubular reactor and heated
to 40.degree. C., and was treated with the introduced carbon
dioxide for 5 h, which was then slowly heated to 80.degree. C. to
dry for 12 h, calcined at 500.degree. C. for 4 h, cooled, and then
reduced at 350.degree. C. with pure hydrogen for 5 hours to obtain
a supported catalyst A-12 containing 8.0 wt % of Ni, 7.0 wt % of
Cu, 0.25 wt % of Pd, 0.05 wt % of Rh and 0.2 wt % of Zr.
EXAMPLE 1-1
The difference from Example 1 is that the metal salt solution was
not further prepared into a metal ammonium salt solution but was
directly used for adsorption of the support; in addition, the
adsorbed wet support is directly subjected to drying, calcination
and reduction treatment. The supported catalyst A-1-1 was
obtained.
COMPARATIVE EXAMPLE 1
The difference from Example 1 is that Rh is not contained in the
mixed solution of the metal ammonium salts. The supported catalyst
D-1 was obtained.
EXAMPLE 13
Amination of Diethylene Glycol (M=106)
A fixed-bed reactor was loaded with supported catalyst A-1 having a
bulk volume of 30 ml. The reaction temperature was raised to
250.degree. C. and the system pressure (absolute pressure, the same
as follows) was raised to 10 MPa, then starting to feed the
reactor. The space velocity of diethylene glycol was 0.3 h.sup.-1,
the molar ratio of liquid ammonia/diethylene glycol was 60:1, and
the molar ratio of hydrogen/diethylene glycol was 1:1. The
reactants were distilled to remove excess ammonia and water, and
analyzed by gas chromatography. The content of diaminodiethylene
glycol was 99.6 wt %, the content of morpholine was 0.4 wt %, and
monoaminodiethylene glycol and diethylene glycol were not detected.
According to the sampling and analysis after 120 h, the result was
unchanged. The conversion rate of the raw material was 100%, and
the yield of the amination product was 99.6%.
EXAMPLE 14
Amination of Dipropylene Glycol (M=134)
A fixed-bed reactor was loaded with supported catalyst A-2 having a
bulk volume of 30 ml. The reaction temperature was lowered to
210.degree. C. and the system pressure was raised to 18 MPa, then
starting to feed the reactor. The space velocity of dipropylene
glycol was 0.75 h.sup.-1, the molar ratio of ammonia/dipropylene
glycol was 30:1, and the molar ratio of hydrogen/dipropylene glycol
was 0.05:1. The reactants were distilled to remove excess ammonia
and water, and analyzed by gas chromatography. The content of
diaminodipropylene glycol was 99.5 wt %, the content of
dimethylmorpholine was 0.5 wt %, and monoaminodipropylene glycol
and dipropylene glycol were not detected. According to the sampling
and analysis after 150 h, the result was unchanged. The conversion
rate of the raw material was 100%, and the yield of the amination
product was 99.5%.
EXAMPLE 15
Amination of Polyether Polyol PPG-230 (Difunctional, Molecular
Weight of 230)
A fixed-bed reactor was loaded with supported catalyst A-3 having a
bulk volume of 30 ml. The reaction temperature was raised to
220.degree. C. and the system pressure was raised to 15 MPa, then
starting to feed the reactor. The space velocity of PPG-230 was 3
h.sup.-1, the molar ratio of liquid ammonia/PPG-230 was 6:1, and
the molar ratio of hydrogen/PPG-230 was 0.5:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of diamination product was 99.8 wt %,
the monoamination product and PPG-230 were not detected, and the
content of dimethylmorpholine was 0.2 wt %. According to sampling
and analysis after 200 h, the result was unchanged. The conversion
rate of the raw material was 100%, and the yield of the amination
product was 99.8%.
EXAMPLE 16
Amination of Polyether Polyol T-2000 (Trifunctional, Molecular
Weight of 2000)
A fixed-bed reactor was loaded with supported catalyst A-4 having a
bulk volume of 30 ml. The reaction temperature was lowered to
180.degree. C., and the system pressure was raised to 12 MPa, then
starting to feed the reactor. The space velocity of T-2000 was 0.5
h.sup.-1, the molar ratio of liquid ammonia/T-2000 was 20:1, and
the molar ratio of hydrogen/T-2000 was 0.7:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of triamination product was 99.7 wt %,
the diamination product, monoamination product and T-2000 were not
detected, and the content of dimethylmorpholine was 0.3 wt %.
According to the sampling and analysis after 200 h, the result was
unchanged. The conversion rate of the raw material was 100%, and
the yield of the amination product was 99.7%.
EXAMPLE 17
Amination of Polyether Polyol D-5000 (Difunctional, Molecular
Weight of 5000)
A fixed-bed reactor was loaded with supported catalyst A-5 having a
bulk volume of 30 ml. The reaction temperature was lowered to
150.degree. C., and the system pressure was raised to 16 MPa, then
starting to feed the reactor. The space velocity of D-5000 was 2.0
h.sup.-1, the molar ratio of liquid ammonia/D-5000 was 13:1, and
the molar ratio of hydrogen/D-5000 was 0.2:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of diamination product was 99.9 wt %,
the monoamination product and D-5000 were not detected, and the
content of dimethylmorpholine was 0.1 wt %. According to the
sampling and analysis after 150 h, the result was unchanged. The
conversion rate of the raw material was 100%, and the yield of the
amination product was 99.9%.
EXAMPLE 18
Amination of Polyether Polyol T-403 (Trifunctional, Molecular
Weight of 400)
A fixed-bed reactor was loaded with supported catalyst A-6 having a
bulk volume of 30 ml. The reaction temperature was raised to
225.degree. C., and the system pressure was raised to 20 MPa, then
starting to feed the reactor. The space velocity of T-403 was 1.5
h.sup.-1, the molar ratio of liquid ammonia/T-403 was 18:1, and the
molar ratio of hydrogen/T-403 was 0.4:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of triamination product was 99.6 wt %,
the diamination product, monoamination product and T-403 raw
material were not detected, and the content of dimethylmorpholine
was 0.4 wt %. According to the sampling and analysis after 150 h,
the result was unchanged. The conversion rate of the raw material
was 100%, and the yield of the amination product was 99.6%.
EXAMPLE 19
Methylation of Polyether Polyol D-400 (Difunctional, Molecular
Weight of 400)
A fixed-bed reactor was loaded with supported catalyst A-7 having a
bulk volume of 30 ml. The reaction temperature was lowered to
190.degree. C., and the system pressure was raised to 15 MPa, then
starting to feed the reactor. The space velocity of D-400 was 0.1
h.sup.-1, the molar ratio of methylamine/D-400 was 10:1, and the
molar ratio of hydrogen/D-400 was 0.35:1. The reactants were
distilled to remove excess methylamine and water, and analyzed by
gas chromatography. The content of di(methylamination) product was
99.8 wt %, the mono(methylamination) product and D-400 raw material
were not detected, and the content of others were 0.2 wt % totally.
According to the sampling and analysis after 150 h, the result was
unchanged. The conversion rate of the raw material was 100%, and
the yield of the amination product was 99.8%.
EXAMPLE 20
Dimethylation of Polyether Polyol D-2000 (Difunctional, Molecular
Weight of 2000)
A fixed-bed reactor was loaded with supported catalyst A-8 having a
bulk volume of 30 ml. The reaction temperature was lowered to
230.degree. C., and the system pressure was raised to 5 MPa, then
starting to feed the reactor. The space velocity of D-2000 was 0.5
h.sup.-1, the molar ratio of dimethylamine/D-2000 was 15:1, and the
molar ratio of hydrogen/D-2000 was 0.1:1. The reactants were
distilled to remove excess dimethylamine and water, and analyzed by
gas chromatography. The content of di(dimethylamination) product
was 99.7 wt %, the mono(dimethylamination) product and D-2000 raw
material were not detected, and the content of others were 0.3 wt %
totally. According to the sampling and analysis after 150 h, the
result was unchanged. The conversion rate of the raw material was
100%, and the yield of the amination product was 99.7%.
EXAMPLE 21
Amination of Polyether Polyol D-600 (Difunctional, Molecular Weight
of 600)
A fixed-bed reactor was loaded with supported catalyst A-9 having a
bulk volume of 30 ml. The reaction temperature was lowered to
165.degree. C., and the system pressure was raised to 13 MPa, then
starting to feed the reactor. The space velocity of D-600 was 0.6
If', the molar ratio of liquid ammonia/D-600 was 16:1, and the
molar ratio of hydrogen/D-600 was 0.25:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of diamination product was 99.9 wt %,
the monoamination product and D-600 were not detected, and the
content of dimethylmorpholine was 0.1 wt %. According to the
sampling and analysis after 160 h, the result was unchanged. The
conversion rate of the raw material was 100%, and the yield of the
amination product was 99.9%.
EXAMPLE 22
Methylation of Polyether Polyol D-600 (Difunctional, Molecular
Weight of 600)
A fixed-bed reactor was loaded with supported catalyst A-10 having
a bulk volume of 30 ml. The reaction temperature was raised to
215.degree. C., the system pressure was raised to 17 MPa, then
starting to feed the reactor. The space velocity of D-600 was 0.6
h.sup.-1, the molar ratio of methylamine/D-600 was 19:1, and the
molar ratio of hydrogen/D-600 was 0.15:1. The reactants were
distilled to remove excess methylamine and water, and analyzed by
gas chromatography. The content of di(methylamination) product was
99.8 wt %, the mono(methylamination) product and D-600 raw material
were not detected, and the content of others were 0.2 wt % totally.
According to the sampling and analysis after 180 h, the result was
unchanged. The conversion rate of the raw material was 100%, and
the yield of the amination product was 99.8%.
EXAMPLE 23
Dimethylation of Polyether Polyol D-600 (Difunctional, Molecular
Weight of 600)
A fixed-bed reactor was loaded with supported catalyst A-11 having
a bulk volume of 30 ml. The reaction temperature was lowered to
200.degree. C., and the system pressure was raised to 18 MPa, then
starting to feed the reactor. The space velocity of D-600 was 1.0
h.sup.-1, the molar ratio of dimethylamine/D-600 was 12:1, and the
molar ratio of hydrogen/D-600 was 0.3:1. The reactant was distilled
to remove excess dimethylamine and water, and analyzed by gas
chromatography. The content of di(dimethylamination) product was
99.6 wt %, the mono(dimethylamination) product and D-600 raw
material were not detected, and the content of others were 0.4 wt %
totally. According to the sampling and analysis after 120 h, the
result was unchanged. The conversion rate of the raw material was
100%, and the yield of the amination product was 99.6%.
EXAMPLE 24
Amination of Polyether Polyol T-3000 (Trifunctional, Molecular
Weight of 3000)
A fixed-bed reactor was loaded with supported catalyst A-12 having
a bulk volume of 30 ml. The reaction temperature was lowered to
180.degree. C., and the system pressure was raised to 16 MPa, then
starting to feed the reactor. The space velocity of T-3000 was 0.5
h.sup.-1, the molar ratio of liquid ammonia/T-3000 was 18:1, and
the molar ratio of hydrogen/T-3000 was 0.35:1. The reactants were
distilled to remove excess ammonia and water, and analyzed by gas
chromatography. The content of diamination product was 99.7 wt %,
the monoamination product and T-3000 raw material were not
detected, and the content of dimethylmorpholine was 0.3 wt %.
According to the sampling and analysis after 210 h, the result was
unchanged. The conversion rate of the raw material was 100%, and
the yield of the amination product was 99.7%.
EXAMPLE 25
The difference from Example 13 was that the reaction was carried
out using Catalyst A-1-1.
Upon detection, the reaction results were as follows: the content
of diaminodiglycol was 92.6 wt %, the content of morpholine was 2.1
wt %, the content of monoaminodiglycol was 5.3 wt %, and diglycol
were not detected. According to the sampling and analysis after 120
h, the result was unchanged. The conversion rate of the raw
material was 100%, and the yield of amination product was
90.6%.
COMPARATIVE EXAMPLE 2
The difference from Example 13 was that the reaction was carried
out using Catalyst D-1.
Upon detection, the reaction results were as follows: the content
of diaminodiglycol was 93.6 wt %, the content of morpholine was 1.4
wt %, the content of monoaminodiglycol was 5.0 wt %, and diglycol
was not detected. According to the sampling and analysis after 120
h, the result was unchanged. The conversion rate of the raw
material was 100%, and the yield of the amination product was
90.6%.
COMPARATIVE EXAMPLE 3
The catalyst was prepared according to the method described in
Example 1 of CN102336903A by reacting a NaOH solution with a Ni--Al
alloy. By adjusting the amount of NaOH added, the prepared catalyst
had a Ni content of 90 wt % and an Al content of 10 wt %. The
catalyst was evaluated according to the amination of polyether
polyol PPG-230 (difunctional, molecular weight of 230) in Example
15 of the present application. Using gas chromatography to analyze
the reaction products: the content of diamination product was 90.5
wt %, the content of monoamination product was 2.0 wt %, the
content of dimethylmorpholine was 2.5 wt %, and the content of raw
material was 5.0 wt %. According to the sampling and analysis after
50 h, the result was unchanged. The conversion rate of the raw
material was 95%, and the yield of the amination product was
92.5%.
COMPARATIVE EXAMPLE 4
The catalyst was prepared according to the method described in
Example 1 of CN102336903A by reacting a NaOH solution with a Ni--Al
alloy. By adjusting the amount of NaOH added, the prepared catalyst
had a Ni content of 95 wt % and an Al content of 5 wt %. The
catalyst was evaluated according to the amination of polyether
polyol T-403 (trifunctional, molecular weight of 400) in Example 18
of the present application. Using gas chromatography to analyze the
reaction products: the content of triamination product was 85.6 wt
%, the content of diamination product was 3.4 wt %, the content of
monoamination product was 2.0 wt %, the content of
dimethylmorpholine content was 1.0 wt %, and the content of raw
material T-403 was 8.0 wt %. According to the sampling and analysis
after 100 h, the result was unchanged. The conversion rate of the
raw material was 92%, and the yield of the amination product was
91.0%.
Conclusion: It can be seen from the above description that the
specific combination of the active components of nickel, copper,
palladium and rhodium in the catalyst of the present invention can
greatly reduce by-products in the amination process of polyether
polyol (eg, monoamino and/or bisamino by-products,
dimethylmorpholine by-products generated by low molecular weight
polyethers, etc.), especially under the conditions that the
polyether polyol is completely converted, thereby greatly improving
the selectivity and product yield of primary amines.
* * * * *